JPH0610194B2 - Viologen derivative and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel viologen derivative and a method for producing the same. More specifically, the present invention relates to a novel viologen derivative in which a vinyl group having a polymerizing ability is directly bonded to a viologen skeleton and a method for producing the same.

[Problems to be Solved by Prior Art and Invention]

A viologen derivative can be easily reversibly oxidized / reduced under various conditions, and its reductant has attracted attention because it is colored.
Utilization for redox mediators and various sensors has been proposed, and various derivatives and oligomers have been produced.

Among them, the low molecular weight viologen derivative has shortcomings such as short cycle life, slow response speed and short memory life when used for display materials and the like. Further, it has been pointed out that the absorption wavelength is short for applications such as photosensitive materials.

As a method for solving these problems, various oligomers or polymers having a viologen group have been proposed.
Among them, there are roughly classified into those having a viologen group in the main chain and those having a side chain (pendant). The former is
Although the redox repeating performance is slightly improved, the electron transfer rate is significantly reduced, and sufficient film performance cannot be obtained when used as a film material. The latter has a problem that although the electron transfer rate is improved, the redox repeatability is deteriorated.

On the other hand, a viologen monomer having a double bond has been attracting attention because it can be modified in various ways due to its polymerizing ability, but the monomers proposed up to now have a long pendant spacer, and therefore the above-mentioned problems occur. I couldn't overcome it.

Therefore, the purpose of the present invention is. It is intended to provide a novel viologen derivative which solves the above problems.

[Means for solving problems]

The present invention achieves the above object by a novel viologen derivative represented by the following general formula (I).

Here, R represents a hydrogen atom or an aliphatic group having 1 to 6 carbon atoms, and examples of such an aliphatic group include an alkyl group, an alkenyl group, and -O-, -S-, -CO-, -SO.
_{-, - SO 2 -, -} COO -, - NH- 2 divalent one bond is formed by bonding an aliphatic group of groups such as, such an aliphatic group or a halogen, -OH, substituted by -COOH, etc. And an alkyl group or an alkenyl group, and preferably -C
_{H 3, -C 2 H 5,} C 3 H 7, -C 4 H 9 such as an alkyl group and _-S-CH 3 _{of, -O-C 2 H 5,} -COOC 3,
_{-OCOCH 3, -C 2 H 4 -O} -CH 3, -CH 2 O
It is an aliphatic group containing a hetero atom in the main chain such as COCH ₃ .

R'represents a hydrogen atom, an aliphatic group or an aromatic group, and examples of such an aliphatic or aromatic group include an alkyl group, an alkenyl group, a phenyl group, an alkyl-substituted phenyl group, a tolyl group, a naphthyl group, an anthryl group and benzyl. Group, cycloalkyl group, cycloalkenyl group, and -O-, -S
-, - CO -, - SO -, - SO 2 -, - COO -, -
Substituted with a group in which one bond of a divalent group such as NH- is bonded, or halogen, -OH, -COOH,-
SH, various aliphatic or aromatic groups of the substituted by -NO _2, and the like, preferably _-CH 3, -C
_{2 H 5, -C 3 H 7} , alkyl groups such as _-C 4 _{H 9, -C
H = CH 2, -C (R} ) = CH 2 and the like alkenyl groups, phenyl group, a benzyl group, a tolyl group, for example _-CH 2 CO
_{CH 3, -C 2 H 4 OC} 2 H 5, -C 2 H 4 SCH 3,
Examples thereof include an aliphatic or aromatic group containing a hetero atom such as —C ₆ H ₄ —COOCH ₃ and a cyclohexyl group.

▲ X ₁▼, ▲ X _Two▼ is dipyridinium and stable salt
It can be any anion that forms
Yes. Halogen ions (Cl , B
r , I ) And CH_Three ▲ CO _Two▼ 、 ▲ HSO
_Four▼, CF_Three ▲ CO _Two▼ 、 ▲ FSO _Three▼, CH
_Three ▲ SO _Three▼ 、 ▲ BF _Four▼, ▲ PF ₆▼, ▲ Cl
O _Four▼ 、 ▲ AsF ₆▼ 、 ▲ SbF ₆▼ and others, poly
Anions supported by the mer are included.

Specific examples of the novel viologen derivative of the present invention represented by the general formula (I) include compounds having the following structures.

The novel viologen derivative of the present invention represented by the general formula (I) can be produced by reacting a compound represented by the following general formula (II) with a base for dehydrohalogenation.

In the formula, R and R'are as defined in the general formula (I).
Is the same as Y is a halogen atom (Cl , Br ，
I ). ▲ X _Three▼ and ▲ X _Four▲ is the same or different
Which may be an anion, and has the general formula (I)
Defined by ▲ X ₁▼, ▲ X _TwoUse the anion of ▼
can do.

The compound represented by the general formula (II) can be obtained in a high yield by the reaction of the corresponding halogenated hydrocarbon derivative and the dipyridyl derivative (for example, the following formulas (III) and (IV)).

As the base used in the production method of the present invention, a reagent capable of performing a usual dehydrohalogenation reaction is used. In particular, since the compound represented by the general formula (II) is sensitive to the dehydrohalogenation reaction, a weakly basic base is also used. As such a base, an inorganic base such as NaOH, KOH or LiOH, or a usual base such as amine, amine-anion or alkoxide can be used.

The dehydrohalogenation reaction does not particularly require heating and proceeds under mild conditions. Depending on the type of base, a reaction of decomposing the viologen structure is observed as a side reaction with dehydrohalogenation, so the reaction is carried out at the lowest temperature, usually 0 to -50 ° C, as long as the time permits. A polar solvent such as alcohol or water is used as a reaction solvent for this dehydrohalogenation reaction.

Since the novel viologen derivative of the present invention has a double bond, it can be used as a monomer for polymerization. The polymerization can be carried out by homopolymerization using an ordinary radical initiator or by copolymerization with another copolymerizable monomer. It is also useful as a monomer for plasma polymerization, radiation polymerization and the like.

Examples of such a copolymerizable monomer include ethylene,
Propylene, isobutylene, pentene, hexene-1,
Mono-olefins such as 4-methylpentene-1, butene-1; for example, butadiene, 2-methyl-1,3-butadiene, 1,4-hexadiene, 2,3-dimethyl-1,
Diolefins such as 3-butadiene; for example, vinyl chloride, vinyl fluoride, vinylidene chloride, vinyl bromide, trichloroethylene, tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, hexafluoropropylene, chloroprene, 2,3-dichloro -1,3
Halogenated olefins such as butadiene and halogenated diolefins; unsaturated alcohols such as vinyl alcohol, allyl alcohol; methyl vinyl ether, isobutyl vinyl ether, isopropyl vinyl ether, other alkyl vinyl ethers, alkyl allyl ethers, alkyl methacryl ethers , Unsaturated ethers such as polyoxyalkylene glycol (meth) allyl ether; unsaturated aldehydes and unsaturated ketones such as acrolein, methacrolein, crotonaldehyde, methyl vinyl ketone; vinyl acetate, vinyl propionate, birch sack Vinyl esters such as vinyl acrylate, vinyl chloroacetate, vinyl cinnamate; diallyl orthophthalate, diallyl isophthalate, diallyl Allyl esters such as 2,6-naphthalene dicarboxylate; such as acrylonitrile, unsaturated nitriles such as methacrylonitrile; for example, acrylic acid, methacrylic acid, crotonic acid, maleic acid,
Unsaturated carboxylic acids such as maleic anhydride and itaconic acid;
For example, unsaturated carboxylic acid esters such as alkyl acrylate, alkyl methacrylate, alkyl maleate and alkyl itaconic acid; unsaturated amides such as acrylamide, N, N-dimethylacrylamide, N-alkylol acrylamide and methacrylamide; For example, styrene, α-methylstyrene, divinylbenzene, oxystyrene, vinylbenzyl chloride, p-hydroxystyrene, N-vinylcarbazole, 1-vinyl-2-
Methyl-imidazole, 2-vinylimidazole, 2-
Vinylimidazoline, N-vinylcaprolactam, acryloylmorpholine, N-vinylpyrrolidone, vinylpyridine, cinnamoylmethylstyrene, acryloylmorpholine, dialkylaminomethyl-p-hydroxystyrene, vinylbenzyl-trialkylammonium chloride, p-vinylbenzenesulfonic acid Carbon such as salt
Cyclic compounds having a carbon double bond; examples thereof include other monomers such as vinyl isocyanate, vinyl urethane, vinyl sulfonic acid, methoxymethyl vinyl sulfide, vinyl-N, N-dialkyldithiocarbamate, and divinyl sulfone. it can.

Hereinafter, the effectiveness of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded.

Example 1 Synthesis of 1-propyl-1'-vinyl-4,4'-dipyridinium dibromide (1) 1-Propyl-1'-bromoethyl-4,4'-dipyridinium dibromide 1,2-dibromoethane 15.4 ml (0.18 mol) was dissolved in 25 ml of dimethylformamide, heated to 100 ° C., and then 5 g (0.018 mol) of 1-propyl-4- (4-pyridyl) pyridinium bromide was added to dimethylformamide. Add 75 ml of solution slowly and add 2 more
Stir for 4 hours at 100 ° C. The precipitated orange crystals were collected by filtration and washed with hot ether. The crystals were recrystallized from 99% ethanol to give 1-propyl-1'-bromoethyl-4,4 'as a yellow crystalline powder having the following analysis results.
-6.9 g of dipyridinium dibromide were obtained.

(result of analysis)
-Mp 223.5-224.
5 ℃ ・ IR ▲ ν ^KBr _max ▼: 3000, 1638, 1560, 1508, 1455, 1380, 134
5, 1265, 1235, 1220, 1195, 1170, 940, 890, 860, 830, 715, 55
0,490 cm ^-1 NMR (D ₂ O) Internal standard: 2,2-dimethyl-2-silapentane-5
Sodium sulfonate δ; 1.0 (3H, t), 2.3 (2H, q), 4.Q (2
H, t), 4.6 (2H, t), 5.2 (2H, t), 8.6
(4H, m), 9.2 (4H, m) Elemental analysis As C ₁₅ H ₁₉ N ₂ Br ₃ (2) 1-Propyl-1′-vinyl-4,4′-dipyridinium dibromide 1-propyl-1′-bromoethyl-4,4′-dipyridinium dibromide 4 g (0 .0
40 mol of a mixed solution of methanol and water (3: 1)
And then cooled to -10 ° C, and then -10 ° C to -15
Keeping at ℃, 10N sodium hydroxide solution 0.86
ml (0.009 mol) was gradually added dropwise, and the mixture was further stirred for 70 minutes. After the reaction, adjust the pH to 4 with 48% hydrobromic acid,
The solvent was distilled off under reduced pressure to obtain a yellow powder. 99 of this powder
Recrystallized from ethanol to give 1-propyl-1'-vinyl-4,4'-yellow crystalline powder having the following analytical results.
2.5 g of dipyridinium dibromide was obtained.

(Analysis result) ・ mp 203 to 204 ° C. ・ IR ▲ ν ^KBr _max ▼: 2980, 1640, 1625, 1550, 1510, 1450, 142
0, 1360, 1265, 1255, 1230, 1200, 1175, 1110, 965, 940, 850, 8
30, 795, 755, 725, 725, 480 cm ^-1 · NMR (CD ₃ OD) Internal standard: tetramethylsilane δ; 1.1 (2H, t), 2.2 (2H, m), 4.8 (2
H, t), 6.1 (1H, m), 6.5 (1H, dd), 7.
9 (1H, q), 8.9 (4H, m), 9.5 (4H, m) .UV (H ₂ O) λ _max : 270 nm Example 2 1,1′-divinyl-4,4′- Synthesis of dipyridinium dibromide (1) 1,1'-Dibiromoethyl-4,4'-dipyridinium dibromide 1,2-dibromoethane 41.3 ml (0.48 mol) was dissolved in dimethylformamide 18 ml, and 100 ° C. After warming to 55 ° C., 55 g of dimethylformamide (2 g, 0.013 mol) of 4,4′-bipyridine was gradually added dropwise thereto, and the mixture was further stirred for 24 hours. The deposited yellow precipitate was collected by filtration and washed with hot ether. The precipitate was recrystallized from 99% ethanol to give a yellow crystalline powder having the following analytical results:
1.6 g of 1'-dibromoethyl-4,4'-dipyridinium dibromide was obtained.

(Analysis result) ・ mp 245 to 247 ° C. ・ IR ▲ ν ^KBr _max ▼: 3000, 1635, 1555, 1510, 1450, 1365, 130
5, 1255, 1230, 1195, 1170, 830, 805, 770, 740, 720, 675, 555,
490 cm ^-1 · NMR (D ₂ O) Internal standard: 2,2, -dimethyl-2-silapentane-5
-Sodium sulfonate δ; 4.2 (4H, t), 5.3 (4H, t), 8.6 (4
H, m), 9.2 (4H, m) (2) 1,1'-divinyl-4,4'-dipyridinium
Dibromide 1,1′-dibromoethyl-4 obtained in (1) above,
1.6 g of 4'-dipyridinium dibromide (0.00
2 mol) was dissolved in 20 ml of a mixed solution of methanol-water (3: 1) and cooled to -10 ° C. -10 ℃ ~ -15 ℃
Keeping at 10 ml of 10N sodium hydroxide solution 0.1 ml
(0.001 mol) was gradually added dropwise, and the mixture was further stirred for 70 minutes. After the reaction, the pH was adjusted to 4 with 48% hydrobromic acid, and then the solvent was distilled off under reduced pressure to obtain a yellow powder. 99% of this powder
The mixture was added to 100 ml of ethanol and heated to 50 ° C., the remaining solid was collected by filtration, and recrystallized from 99% ethanol to give 1,1′-divinyl-yellow crystalline powder having the following analytical results.
0.7 g of 4,4'-dipyridinium dibromide was obtained.

(Analysis result) ・ mp 244 to 246 ° C. ・ IR ▲ ν ^KBr _max ▼: 2980, 1640, 1630, 1550, 1510, 1450, 142
0, 1360, 1265, 1255, 1230, 1200, 1175, 1110, 965, 940, 845, 8
30, 795, 755, 725, 480 cm ^-1 · NMR (D ₂ O) Internal standard: 2,2, -dimethyl-2-silapentane-5
-Sodium sulfonate δ; 6.1 (4H, d), 6.4 (2H, dd), 7.7 (2
H, dd), 8.8 (4H, m), 9.3 (4H, m) UV λ _max : 290 nm Example 3 1-Propyl-1′-vinyl-4,4′-dipyridinium diverchlorate Synthesis of 1-propyl-1′-vinyl-4, synthesized in Example 1
4'-dipyridinium dibromide 2.0 g (0.005
Mol) was dissolved in 50 ml of ethanol, and 5 ml of 60% perchloric acid was added dropwise. The precipitated ocher precipitate was collected by filtration and recrystallized from ethanol to obtain 1.2 g of 1-propyl-1'-vinyl-4,4'-dipyridinium diverchlorate having the following analysis result.

(Analysis result) ・ mp 228.5 to 229.5 ° C. ・ IR ▲ ν ^KBr _max ▼: 3020, 1645, 1630, 1560, 1510, 1450, 141
5, 1360, 1305, 1260, 1230, 1200, 1000-1180, 950, 845, 835,
810, 750, 725, 580, 530, 520, 480cm ^-1 Example 4 Synthesis of 1-propyl-1′-vinyl-4,4′-dipyridinium difluoroborate 1-propyl-1′-vinyl-4, synthesized in Example 1
2.5 g of 4'-dipyridinium dibromide (0.006
Mol) in 100 ml of methanol and silver borofluoride 2.
5 g (0.013 mol) of a methanol solution (100 ml) was added dropwise, and the resulting white precipitate of silver bromide was filtered off. The filtrate was partially concentrated and cooled to obtain an ocher crystalline powder. This powder was recrystallized from 99% ethanol and 1-propyl-1'-vinyl-4,4 'having the following analytical results was obtained.
1.2 g of dipyridinium difluoroborate were obtained.

(Analysis result) ・ mp 228.5 to 229.5 ° C. ・ IR ▲ ν ^KBr _max ▼: 3010, 1645, 1635, 1560, 1510, 1450, 141
5, 1360, 1305, 1260, 1230, 1200, 1020 to 1170, 950, 845, 835,
810, 750, 725, 580, 530, 520, 480 cm ^-1 Reference Example 1 Synthesis of copolymer of 1-propyl-1'-vinyl-4,4'-dipyridinium salt and acronitrile Obtained in Example 3 1-propyl-1'-vinyl-4,4 '
-Dipyridinium diverchlorate or 1-propyl-1'-vinyl-4,4'-dipyridinium fluoroborate (0.2-1.2 mmol) obtained in Example 4 and acronitrile (2.4-3). (0.8 mmol) was weighed into a Pyrex polymerization tube, and 1 ml of r-butyrolactone was added and dissolved therein. Azobisisobutyronitrile (1 mol%) was added thereto, and the atmosphere was further replaced with nitrogen gas, which was then degassed and sealed and heated at 80 ° C. for 16 hours. The reaction solution was added dropwise to methanol, and the precipitated precipitate was collected by filtration, dried under reduced pressure, dissolved in dimethylformeamide, and added dropwise to methanol. Ocher powder 1-propyl-1'-vinyl-4,
Copolymer of 4'-dipyridinium diperchlorate and acrylonitrile and 1-propyl-1'-vinyl-
Copolymers of 4,4'-dipyridinium fluoroborate and acrylonitrile were obtained, respectively. The results of these analyzes are shown below.

・ IR (copolymer with perchlorate salt) ▲ ν ^KBr _max ▼: 3650-3350, 2930, 2250, 1640, 1450, 134
0 ~ 1390, 1150, 1120, 1080, 825, 620, 520cm ^-1 · IR (copolymer with fluoroborate salt) ν ^KBr _max : 3700 ~ 3500, 3000, 2250, 1640, 1455, 1380, 135
0, 1270, 1180, 1040 to 1100, 850, 825 cm ^-1 · NMR ((CD ₃ ) ₂ SO) Internal standard: tetramethylsilane δ; 1.0 (t), 2.1, 3.2, 4. 3, 4.7, 8.6, 9.6 From the results of elemental analysis and NMR of the copolymers, the molar ratio of the viologen group and the acrylonitrile group of these copolymers was calculated. The results are shown in Table 1.

The viologen derivatives synthesized in Examples 1 and 2, 1-propyl-1′-vinyl-4,4′-dipyridinium dibromide and 1,1′-divinyl-4,4′-dipyridinium dibromide, were added to 0.1M. -Tris buffer (pH 8.
0) to 0.2M potassium chloride solution to prepare a 1 milliM solution of the viologen derivative. The cyclic voltammogram of the viologen derivative was measured using a saturated calomel electrode as a reference electrode and platinum as a working electrode and a counter electrode. In each case, a two-stage redox wave based on redox with the one-electron reduced form and the two-electron reduced form of viologen was shown, and the redox potentials shown in Table 2 below were obtained.

Reference Example 3 Action of Viologen Copolymer Film-Coated Electrode and Its Cyclic Voltammetry 1-Propyl-1′-vinyl-4, synthesized in Reference Example 1
10 mg of a copolymer of 4'-dipyridinium diverchlorate and acrylonitrile (molar ratio charged: 1:19) was dissolved in 0.5 ml of dimethylformamide and cast on a gold electrode (radius 0.4 cm) whose periphery was insulated with Teflon. Then, the viologen copolymer film-coated gold electrode was prepared by heating at 60 ° C. to remove the solvent. Using this electrode as a working electrode and platinum as a counter electrode, a cyclic voltammogram was measured in a pH 8-0.2M potassium chloride solution, and as a result, a two-stage redox wave (shown in FIG. 1) was obtained (scan rate: 2 × 10 ² mV / sec). In FIG. 1, the solid line shows the redox wave of the first use, and the dotted line shows the redox wave of the 10th use.

Comparative Example 1-Methyl-1′-p-vinylbenzyl-4,4′-dipyridinium salt-acrylonitrile copolymer membrane cyclic gold voltammetry of a gold electrode coated 1-methyl-1 in the same manner as in Reference Example 3 A polymer film-coated electrode of ′ -p-vinylbenzyl-4,4′-dipyridinium salt-acrylonitrile copolymer was prepared, and its cyclic voltammogram was measured. The results are shown in FIG. 2 (scan speed: 2 × 10 ² mV / sec). In FIG. 2, the solid line shows the redox wave of the first use, and the dotted line shows the redox wave of the third use.

〔The invention's effect〕

The novel viologen derivative of the present invention is a light-sensitive / electric-sensitive display material,
It can be used as a photovoltaic material, a mediator of redox reaction, various sensors, and the like. The compound represented by the general formula (I) exhibits high wavelength light absorption and sensitivity to reduction reaction, which are not found in conventional viologen derivatives. Further, the copolymer of the novel viologen derivative of the present invention shows remarkable improvement in stability, and shows resistance to repeated use of the redox reaction which cannot be achieved by conventional oligomers and polymers.

[Brief description of drawings]

FIG. 1 is a graph showing a redox wave obtained by using the viologen copolymer film-coated gold electrode of the present invention prepared in Reference Example 3, and FIG. 2 is a polymer film-coated electrode prepared in Comparative Example. It is a graph which shows the redox wave obtained by using.

Claims (2)

[Claims] 1. A general formula(In the formula, R is a hydrogen atom or an aliphatic group having 1 to 6 carbon atoms,
R'is a hydrogen atom, an aliphatic group or an aromatic group, ▲ X ₁▼ and
And ▲ X _Two▼ may be the same or different anion
Is. ) A vinyl viologen derivative represented by. 2. General formula(In the formula, R is a hydrogen atom or an aliphatic group having 1 to 6 carbon atoms,
R'is a hydrogen atom, an aliphatic group or an aromatic group, ▲ X _Three▼ and
And ▲ X _Four▼ may be the same or different and are anions
And Y is a halogen atom. )
One characterized by performing dehydrohalogenation treatment with a base
General formula(In the formula, R is a hydrogen atom or an aliphatic group having 1 to 6 carbon atoms,
R'is a hydrogen atom, an aliphatic group or an aromatic group, ▲ X ₁▼ and
And ▲ X _Two▼ may be the same or different and are anions
is there. ) A method for producing a vinylviologen derivative represented by
Law.